A Metastable Oxygen Redox Cathode for Lithium‐Ion Batteries
Simultaneously harnessing cation and anion redox activities in the cathode is crucial for the development of high energy-density lithium-ion batteries. However, achieving long-term stability for both mechanisms remains a significant challenge due to pronounced anisotropic volume changes at low lithium content, unfavorable cation migration, and oxygen loss. Here, we demonstrate exceptionally stable cation and anion redox behavior in a metastable, cobalt-free layered oxide, Li<sub>0.693</sub>[Li<sub>0.153</sub>Ni<sub>0.190</sub>Mn<sub>0.657</sub>]O<sub>2</sub> (LLNMO). After 50 cycles at 50 mA/g (~0.2 C), the cathode retains 97.4 % of its initial capacity (222.4 mAh/g) with negligible voltage decay. This remarkable stability is attributed to its metastable O6-type structure (R-3m symmetry) with unique local geometry. The face-sharing connectivity between lithium layers and alternating transition metal (TM) layers effectively suppresses TM migration-induced voltage decay during anion redox. Additionally, the structure balances interlayer cation/cation and anion/anion repulsions, resulting in minimal expansion and contraction during de-/lithiation (<2.3 % along the c-axis) and excellent structural reversibility. These findings highlight that layered oxides with a metastable framework are promising cathode candidates for next-generation ultra-high-energy lithium-ion batteries.
Authors
- Ning Qin (ORCID: https://orcid.org/0000-0003-2543-8351)
- Wilgner Lima da Silva (ORCID: https://orcid.org/0000-0002-1872-6817)
- Joshua M. Stratford (ORCID: https://orcid.org/0000-0002-6867-4226)
- Zhouguang Lu (ORCID: https://orcid.org/0000-0003-3769-9356)
- R. M. Benito (ORCID: https://orcid.org/0000-0003-3949-8232)
- Dominic Gardner (ORCID: https://orcid.org/0009-0001-4780-9312)
- Phoebe K. Allan (ORCID: https://orcid.org/0000-0001-9110-1023)
- Sahil Tippireddy (ORCID: https://orcid.org/0000-0002-5383-6966)
- J. B. WILLIAMS
- Qingmeng Gan
- Chun Zeng
- Fangchang Zhang
- Fucai Zhang (ORCID: https://orcid.org/0000-0001-7177-5450)
- Wen Luo (ORCID: https://orcid.org/0000-0002-9886-5461)
- Yingzhi Li (ORCID: https://orcid.org/0000-0002-1241-7335)
- Joshua W. Makepeace (ORCID: https://orcid.org/0000-0002-7107-0845)
- Cheng Li (ORCID: https://orcid.org/0000-0002-6546-6413)
- Yanfang Wang (ORCID: https://orcid.org/0000-0002-5837-7674)
- Hongzhi Wang (ORCID: https://orcid.org/0000-0002-5469-2327)
- Zhiqiang Li (ORCID: https://orcid.org/0000-0002-3283-6385)
- Kaili Zhang (ORCID: https://orcid.org/0000-0002-5926-2019)
- Yulin Cao
Institutions
- City University of Hong Kong (HK)
- Diamond Light Source (GB)
- Southern University of Science and Technology (CN)
- Division of Materials Science and Engineering (AU)
- The Faraday Institution (GB)
- University of Birmingham (GB)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-02-04
- DOI
- https://doi.org/10.1002/anie.202422789
- Citations
- 9
- Primary Topic
- Advancements in Battery Materials
- Type
- article
- Field-Weighted Citation Impact
- 6.57
Funders
- Salt Science Research Foundation
- National Natural Science Foundation of China
- Southern University of Science and Technology
- Engineering and Physical Sciences Research Council